US9306213B2 - Process for producing cathode active material for lithium ion secondary battery - Google Patents
Process for producing cathode active material for lithium ion secondary battery Download PDFInfo
- Publication number
- US9306213B2 US9306213B2 US14/139,952 US201314139952A US9306213B2 US 9306213 B2 US9306213 B2 US 9306213B2 US 201314139952 A US201314139952 A US 201314139952A US 9306213 B2 US9306213 B2 US 9306213B2
- Authority
- US
- United States
- Prior art keywords
- lithium
- composition
- composite oxide
- containing composite
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
Links
- 239000006182 cathode active material Substances 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000008569 process Effects 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 169
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 163
- 239000002131 composite material Substances 0.000 claims abstract description 158
- 239000000203 mixture Substances 0.000 claims abstract description 149
- 150000001450 anions Chemical class 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 28
- 150000001768 cations Chemical class 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 239000010410 layer Substances 0.000 description 81
- 150000001875 compounds Chemical class 0.000 description 54
- 239000002245 particle Substances 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 37
- 239000011572 manganese Substances 0.000 description 30
- 235000002639 sodium chloride Nutrition 0.000 description 26
- 229910019142 PO4 Inorganic materials 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 15
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- -1 organic acid salt Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000006183 anode active material Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910015658 LixMny Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910019689 Nb3(PO4)5 Inorganic materials 0.000 description 2
- 229910019788 NbF3 Inorganic materials 0.000 description 2
- 229910019787 NbF5 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MBDHLQKZIVIDEY-UHFFFAOYSA-N Olivin Natural products COc1cc(C=C(C)/C(=O)c2c(O)cc(O)cc2O)ccc1O MBDHLQKZIVIDEY-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910008243 Zr3(PO4)4 Inorganic materials 0.000 description 2
- 229910007998 ZrF4 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- PIHTXGRVQBTVRE-KFYAXVMHSA-N olivin Chemical compound OC1=CC(O)=C2C(O)=C(C(=O)[C@H]([C@H]([C@H](OC)C(=O)[C@@H](O)[C@@H](C)O)C3)O)C3=CC2=C1 PIHTXGRVQBTVRE-KFYAXVMHSA-N 0.000 description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 2
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- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Definitions
- the present invention relates to a process for producing a cathode active material for a lithium ion secondary battery.
- the present invention further relates to a cathode for a lithium ion secondary battery using a cathode active material for a lithium ion secondary battery obtained by the production process, and a lithium ion secondary battery.
- Lithium ion secondary batteries are widely used for portable electronic instruments such as mobile phones or notebook-size personal computers.
- a cathode active material for a lithium ion secondary battery a composite oxide of lithium with a transition metal, etc. (hereinafter sometimes referred to as lithium-containing composite oxide) such as LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.2 O 2 or LiMn 2 O 4 , is employed.
- cycle characteristic a further improvement in the discharge capacity per unit mass and in the characteristics such that the discharge capacity will not be decreased after charge and discharge cycles are repeatedly carried out.
- rate characteristics a further improvement in the characteristics such that the discharge capacity will not be decreased after discharged at a high discharge rate
- Patent Document 1 discloses a process of dispersing a lithium-containing composite oxide in an aluminum nitrate aqueous solution, adding an ammonium fluoride aqueous solution thereto, followed by filtration, washing and heating to form a covering layer of aluminum fluoride on the surface of the lithium-containing composite oxide.
- both of filtration and washing are carried out, whereby the process is complicated and in addition, a waste disposal treatment is necessary, and thus the process is inferior in the productivity.
- the cathode active material tends to be agglomerated to form coarse particles.
- Patent Document 2 discloses a method of forming a surface treated layer containing an AlPO k compound by dispersing 20 g of a lithium-containing composite oxide to 100 mL of an aqueous dispersion having an amorphous AlPO k phase dispersed in a colloidal form, followed by drying at 130° C. and further by heat treatment.
- a large quantity of energy is required to dry a large amount of water, and at same time, the cathode active material is likely to be agglomerated to form coarse particles in the same manner as above, at the time of drying.
- this method it is difficult to cover the lithium-containing composite oxide with a compound other than an oxide.
- the present invention provides a process for producing a cathode active material for a lithium ion secondary battery by which a cathode active material excellent in the cycle characteristics and the rate characteristics even when discharging is carried out at a high voltage, can be obtained, a cathode for a lithium ion secondary battery using a cathode active material for a lithium ion secondary battery, and a lithium ion secondary battery.
- the present invention provides the following.
- a process for producing a cathode active material for a lithium ion secondary battery which comprises contacting a lithium-containing composite oxide containing Li element and a transition metal element with the following composition (1) and composition (2), and heating them, wherein
- the total amount A (ml/100 g) of composition (1) and composition (2) contacted per 100 g of the lithium-containing composite oxide is in the ratio of 0.1 ⁇ A/B ⁇ 5 based on the oil absorption B (ml/100 g) of the lithium-containing composite oxide:
- composition (1) an aqueous solution containing cation M having at least one metal element (m) selected from the group consisting of Li, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Sn, Sb, Bi, La, Ce, Pr, Nd, Gd, Dy, Er and Yb;
- metal element (m) selected from the group consisting of Li, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Sn, Sb, Bi, La, Ce, Pr, Nd, Gd, Dy, Er and Yb;
- composition (2) an aqueous solution containing anion N having at least one element (n) selected from the group consisting of S, P, F and B, forming a hardly soluble salt when reacted with the cation M.
- a cathode for a lithium ion secondary battery which comprises a cathode active material for a lithium ion secondary battery produced by the production process as defined in any one of [1] to [8], and a binder.
- a lithium ion secondary battery comprising the cathode as defined in [9], an anode and a non-aqueous electrolyte.
- the production process of the present invention it is possible to produce a cathode active material for a lithium ion secondary battery excellent in the cycle characteristics and the rate characteristics even when discharging is carried out at a high voltage, with good productivity. Further, according to the production process of the present invention, filtration and washing are unnecessary, and the lithium-containing composite oxide will not be agglomerate, whereby handling such as stirring is easy, and further, agglomeration is less likely to occur at the time of drying, whereby the productivity is remarkably improved.
- FIG. 1 is a graph illustrating an Example for a process for producing a cathode active material for a lithium ion secondary battery of the present invention, and showing the relation between the liquid amount A of the composition 1 and the composition 2, and the oil absorption B of the lithium-containing composite oxide.
- the process for producing a cathode active material of the present invention is a process for producing a cathode active material for a lithium ion secondary battery, which comprises contacting a lithium-containing composite oxide containing Li element and a transition metal element with the following composition (1) and composition (2), and heating them, wherein
- the total amount A (ml/100 g) of composition (1) and composition (2) contacted per 100 g of the lithium-containing composite oxide is in the ratio of 0.1 ⁇ A/B ⁇ 5 based on the oil absorption B (ml/100 g) of the lithium-containing composite oxide:
- composition (1) an aqueous solution containing cation M having at least one metal element (m) selected from the group consisting of Li, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Sn, Sb, Bi, La, Ce, Pr, Nd, Gd, Dy, Er and Yb;
- metal element (m) selected from the group consisting of Li, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Sn, Sb, Bi, La, Ce, Pr, Nd, Gd, Dy, Er and Yb;
- composition (2) an aqueous solution containing anion N having at least one element (n) selected from the group consisting of S, P, F and B, forming a hardly soluble salt when reacted with the cation M.
- the lithium-containing composite oxide of the present invention contains Li element and a transition metal element.
- transition metal element for example, at least one member selected from the group consisting of Ni, Co, Mn, Fe, Cr, V and Cu may be used.
- the lithium-containing composite oxide is preferably, for example, a compound (i) represented by the following formula (1), a compound (ii) which is an olivin metal lithium salt which is a substance represented by the following formula (2) or a composite thereof, a compound (iii) represented by the following formula (3-1) or a compound (iv) represented by the following formula (4). They may be used alone or in combination of two or more.
- the lithium-containing composite oxide is particularly preferably the compound (iii) in view of a high capacity, most preferably a compound represented by the following formula (3-1).
- Me is at least one member selected from the group consisting of Mg, Ca, Sr, Ba and Al.
- the compound (i) represented by the formula (1) may, for example, be LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 0.5 Ni 0.5 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.85 Co 0.10 Al 0.05 O 2 or LiNi 1/3 Co 1/3 Mn 1/3 O 2 .
- Compound (ii) Li L X x .Y y .O z .F g (2)
- X is Fe(II), Co(II), Mn(II), Ni(II), V(II) or Cu(II), Y is P or Si, 0 ⁇ L ⁇ 3, 1 ⁇ x′ ⁇ 2, 1 ⁇ y′ ⁇ 3, 4 ⁇ z′ ⁇ 12 and 0 ⁇ g ⁇ 1.
- the olivin metal lithium salt (ii) may be LiFePO 4 , Li 3 Fe 2 (PO 4 ) 3 , LiFeP 2 O 7 , LiMnPO 4 LiNiPO 4 , LiCoPO 4 , Li 2 FePO 4 F, Li 2 MnPO 4 F, Li 2 NiPO 4 F, Li 2 CoPO 4 F, Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 NiSiO 4 or Li 2 CoSiO 4 .
- the compound (iii) is a compound represented by the following formula (3-1).
- the representation of the compound represented by the following formula (3-1) is for the compositional formula before charge/discharge or treatments such as activation.
- activation means to remove lithium oxide (Li 2 O) or lithium and lithium oxide from the lithium-containing composite oxide.
- an electrochemical activation method of charging at a voltage higher than 4.4 V or 4.6 V (a value represented by a potential difference with Li + /Li oxidation-reduction potential) may be mentioned.
- a chemical activation method by a chemical reaction using an acid such as sulfuric acid, hydrochloric acid or nitric acid may be mentioned. Li(Li x Mn y Me′ z )O p F q (3-1)
- Me′ is at least one element selected from the group consisting of Co, Ni, Cr, Fe, Al, Ti, Zr and Mg.
- the compound of the formula (3-1) is also characterized by containing Mn in a specific amount, and the proportion of Mn to the total amount of Mn and Me′ is preferably from 0.4 to 0.8, more preferably from 0.55 to 0.75. When Mn is within the above range, the discharge capacity tends to be high.
- q represents the proportion of F, or is 0 when F is not present.
- p is a value determined according to x, y, z and q, and is from 1.9 to 2.1.
- the compositional ratio of the Li element to the total molar amount of the transition metal element is preferably 1.25 ⁇ (1+x)/(y+z) ⁇ 1.75, more preferably 1.35 ⁇ (1+x)/(y+z) ⁇ 1.65, particularly preferably 1.40 ⁇ (1+x)/(y+z) ⁇ 1.55.
- the compositional ratio is within the above range, a cathode material having a high discharge capacity per unit mass when a high discharge voltage of at least 4.6 V is applied, can be obtained.
- the compound (iii) is more preferably a compound represented by the following formula (3-2): Li(Li x Mn y Ni v Co w )O p (3-2)
- the compositional ratio of the Li element to the total amount of Mn, Ni and Co element is 1.2 ⁇ (1+x)/(y+v+w) ⁇ 1.8, preferably 1.35 ⁇ (1+x)/(y+v+w) ⁇ 1.65, more preferably 1.45 ⁇ (1+x)/(y+v+w) ⁇ 1.55.
- the compound (iii) is particularly preferably Li(Li 0.16 Ni 0.17 Co 0.08 Mn 0.59 )O 2 , Li(Li 0.17 Ni 0.17 Co 0.17 Mn 0.49 )O 2 Li(Li 0.17 Ni 0.21 Co 0.08 Mn 0.54 )O 2 , Li(Li 0.17 Ni 14 Co 0.14 Mn 0.55 )O 2 , Li(Li 0.18 Ni 0.12 Co 0.12 Mn 0.58 )O 2 , Li(Li 0.18 Ni 0.16 Co 0.12 Mn 0.54 )O 2 , Li(Li 0.20 Ni 0.12 Co 0.08 Mn 0.60 )O 2 , Li(Li 0.20 Ni 0.16 Co 0.08 Mn 0.56 )O 2 or Li(Li 0.20 Ni 0.13 Co 0.13 Mn 0.54 )O 2 .
- Me′′ is at least one member selected from the group consisting of Co, Ni, Fe, Ti, Cr, Mg, Ba, Nb, Ag and Al.
- the compound (iv) represented by the formula (4) may be LiMn 2 O 4 , LiMn 1.5 Ni 0.5 O 4 , LiMn 1.0 Co 1.0 O 4 , LiMn 1.85 Al 0.15 O 4 or LiMn 1.9 Mg 0.1 O 4 .
- the lithium-containing composite oxide is preferably in the form of particles, and the average particle size (D 50 ) is preferably from 0.03 to 30 ⁇ m, more preferably from 0.04 to 25 ⁇ m, particularly preferably from 0.05 to 20 ⁇ m.
- the average particle size (D 50 ) means a volume-based cumulative 50% size which is a particle size at a point of 50% on an accumulative curve when the accumulative curve is drawn by obtaining the particle size distribution on the volume basis and taking the whole to be 100%.
- the particle size distribution is obtained from the frequency distribution and accumulative volume distribution curve measured by means of a laser scattering particle size distribution measuring apparatus.
- the measurement of particle sizes is carried out by sufficiently dispersing the powder in an aqueous medium by an ultrasonic treatment and measuring the particle size distribution (for example, by means of a laser diffraction/scattering type particle size distribution measuring apparatus Partica LA-950VII, manufactured by HORIBA Ltd).
- the average particle size (D 50 ) is preferably from 3 to 30 ⁇ m, more preferably from 4 to 25 ⁇ m, particularly preferably from 5 to 20 ⁇ m. In a case where the lithium composite oxide is the compound (ii), the average particle size (D50) is preferably from 0.03 to 5 ⁇ m, more preferably from 0.04 to 1 ⁇ m, particularly preferably from 0.05 to 0.5 ⁇ m.
- the specific surface area of the lithium-containing composite oxide is preferably from 0.1 to 30 m 2 /g, particularly preferably from 0.15 to 25 m 2 /g.
- a dense cathode electrode layer having a high capacity can be formed.
- the specific surface area is preferably from 0.1 to 1 m 2 /g, more preferably from 0.15 to 0.6 m 2 /g. In a case where the lithium composite oxide is the compound (iii), the specific surface area is preferably from 0.3 to 10 m 2 /g, more preferably from 0.5 to 5 m 2 /g, particularly preferably from 1 to 4 m 2 /g. In a case where the lithium composite oxide is the compound (ii), the specific surface area is preferably from 1 to 30 m 2 /g, more preferably from 10 to 25 m 2 /g.
- a method for producing the lithium-containing composite oxide As a method for producing the lithium-containing composite oxide, a method of mixing a precursor of the lithium-containing composite oxide obtained by a coprecipitation method (a coprecipitated composition) and a lithium compound, followed by firing, a hydrothermal synthesis method, a sol-gel method, a dry mixing method (solid phase method), an ion exchange method or a glass crystallization method may properly be employed.
- a method of mixing a precursor of the lithium-containing composite oxide obtained by a coprecipitation method and a lithium compound followed by firing.
- the composition (1) in the present invention is an aqueous solution containing cation M having at least one metal element (m) selected from the group consisting of Li, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Sn, Sb, Bi, La, Ce, Pr, Nd, Gd, Dy, Er and Yb (hereinafter sometimes referred to as metal element (m)).
- the cation M may be an ion of the metal element (m) or may be a complex ion having the metal element (m). In view of the reactivity with the anion N, the cation M is preferably an ion of the metal element (m).
- the metal element (m) is preferably Al, and the cation M is preferably Al 3+ .
- the composition (1) is preferably a solution having a water soluble compound (1) having the metal element (m) and forming the cation M in the aqueous solution, dissolved.
- water soluble means a solubility (the mass [g] of a solute dissolved in 100 g of a saturated solution) in distilled water at 25° C. of higher than 2.
- solubility is higher than 2
- the amount of the cation M contained in the composition (1) can be made large, whereby the after-mentioned covering layer (I) can efficiently be formed.
- the solubility of the water soluble compound (1) is more preferably higher than 5, particularly preferably higher than 10.
- the water soluble compound (1) may, for example, be an inorganic salt such as nitrate, sulfate or chloride, an organic salt or an organic complex such as acetate, citrate, maleate, formate, lactate or oxalate, or an amine complex, of the metal element (m).
- an inorganic salt such as nitrate, sulfate or chloride
- an organic salt or an organic complex such as acetate, citrate, maleate, formate, lactate or oxalate, or an amine complex, of the metal element (m).
- a nitrate, an organic acid salt, an organic complex or an ammonium complex which is likely to be decomposed by heat and which has high solubility in a solvent.
- the water soluble compound (1) is preferably aluminum nitrate, aluminum acetate, aluminum oxalate, aluminum citrate, aluminum lactate, basic aluminum lactate or aluminum maleate.
- the total amount of the metal element M contained in the composition (1) is preferably within a range of from 0.001 to 0.05, more preferably from 0.003 to 0.04, particularly preferably from 0.005 to 0.03, based on the total amount of the transition metal element contained in the lithium-containing composite oxide.
- composition (2) in the present invention is an aqueous solution containing anion N having at least one element (n) selected from the group consisting of S, P, F and B (hereinafter sometimes referred to as element (n)), forming a hardly soluble salt when reacted with the cation M.
- element (n) selected from the group consisting of S, P, F and B
- composition (2) is preferably one having a water soluble compound (2) having the element (n) and forming the anion N when dissociated in an aqueous solution, dissolved.
- Water-soluble here also means a solubility (the mass [g] of a solute dissolved in 100 g of a saturated solution) in distilled water at 25° C. of higher than 2, in the same manner as in the case of the composition (1).
- solubility of the water soluble composition (2) is higher than 2, the amount of the anion N contained in the composition (2) can be made large, whereby the covering layer (I) can efficiently be formed.
- the solubility of the water soluble compound (2) is more preferably higher than 5, particularly preferably higher than 10.
- the anion N may, for example, be specifically SO 4 2 ⁇ , SO 3 2 ⁇ , S 2 O 3 2 ⁇ , SO 6 2 ⁇ , SO 8 2 ⁇ , PO 4 3 ⁇ , P 2 O 7 4 ⁇ , PO 3 3 ⁇ , PO 2 3 ⁇ , F ⁇ , BO 3 3 ⁇ , BO 2 ⁇ , B 4 O 7 2 ⁇ or B 5 O 8 ⁇ .
- SO 4 2 ⁇ , PO 4 3 ⁇ or F ⁇ is particularly preferred.
- the water soluble compound (2) is a compound which has the element (n) and which can form a hardly soluble salt when reacted with the cation M, and may, for example, be an acid such as H 2 SO 4 , H 2 SO 3 , H 2 S 2 O 3 , H 2 SO 6 , H 2 SO 8 , H 3 PO 4 , H 4 P 2 O 7 , H 3 PO 3 , H 3 PO 2 , HF, H 3 BO 3 , HBO 2 , H 2 B 4 O 7 or HB 5 O 8 , or a salt thereof, such as an ammonium salt, an amine salt, a lithium salt, a sodium salt or a potassium salt.
- an acid such as H 2 SO 4 , H 2 SO 3 , H 2 S 2 O 3 , H 2 SO 6 , H 2 SO 8 , H 3 PO 4 , H 4 P 2 O 7 , H 3 PO 3 , H 3 PO 2 , HF, H 3 BO 3 , HBO 2 , H 2 B 4 O 7 or
- a salt rather than an acid.
- an ammonium salt which is decomposed and removed when heated.
- preferred is (NH 4 ) 2 SO 4 , (NH 4 )HSO 4 , (NH 4 ) 3 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 )H 2 PO 4 , NH 4 F or the like.
- the amount (molar ratio) of the anion N contained in the composition (2) is preferably within a range of from 0.001 to 0.05, more preferably from 0.003 to 0.04, particularly preferably from 0.005 to 0.03, based on the total amount of the transition metal element contained in the lithium-containing composite oxide.
- the total amount of the cation M contained in the composition (1) ⁇ the average valence of the cation M)/(the total amount of the anion N contained in the composition (2) ⁇ the average valence of the anion N) is preferably from 0.1 to 10, more preferably from 0.2 to 4, particularly preferably from 0.3 to 2. Within this range, the lithium ion secondary battery will be excellent in the cycle characteristics and the rate characteristics.
- the charge and discharge efficiency will improve, and accordingly it is preferably from 0.1 to 0.99, more preferably from 0.2 to 0.9, particularly preferably from 0.3 to 0.8. It is considered that since the negative charge by the anion N is more significant than the positive charge by the cation M, excess lithium ions contained in the lithium-containing composite oxide are bonded to the anion N, whereby the charge and discharge efficiency will improve.
- water may be used, and a water soluble alcohol or a polyol may be added within a range not to impair the solubility of the water soluble compound (1) and the water soluble compound (2).
- the water soluble alcohol may be methanol, ethanol, 1-propanol or 2-propanol.
- the polyol may be ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, butanediol or glycerin.
- the total content of the water soluble alcohol and polyol contained in the solvent is preferably from 0 to 20 mass %, more preferably from 0 to 10 mass % to the entire amount of the solvent.
- the solvent particularly preferably consists solely of water, in view of the safety, the environment, the handling efficiency and the cost.
- Each of the composition (1) and the composition (2) may further contain a pH adjusting agent so as to adjust the solubility of the water soluble compound (1) and the water soluble compound (2).
- the pH adjusting agent is preferably one which is volatilized or decomposed at the time of heating. Specifically, it is preferably an organic acid such as acetic acid, citric acid, lactic acid, formic acid, maleic acid or oxalic acid, or ammonia.
- a pH adjusting agent which is volatilized or decomposed is used, impurities hardly remain, whereby favorable battery characteristics are likely to be obtained.
- the pH of each of the composition (1) and the composition (2) is preferably from 2 to 12, more preferably from 3 to 11, particularly preferably from 4 to 10.
- the pH is within the above range, elution of the Li element and the transition metal from the lithium-containing composite oxide tends to be small when the lithium-containing composite oxide is contacted with the composition (1) and the composition (2), and further, the amount of impurities such as the pH adjusting agent tends to be small, whereby favorable battery characteristics are likely to be obtained.
- a spray coating method to contact the lithium-containing composite oxide with the composition (1) and the composition (2), particularly preferred is a spray coating method.
- the spray coating method is a simple process, and by this process, the surface of the lithium-containing composite oxide can uniformly be covered with the after-mentioned covering layer (I).
- the composition (1) may be contacted with the lithium-containing composite oxide and then the composition (2) is contacted, the composition (2) may be contacted and then the composition (1) is contacted, the composition (1) and the composition (2) may be alternately contacted several times, or the composition (1) and the composition (2) may be contacted simultaneously.
- the composition (1) is contacted with the lithium-containing composite oxide and then the composition (2) is contacted, whereby the reaction of the cation M and the anion N is likely to proceed.
- the concentration of the water soluble compound (1) contained in the composition (1) is preferably higher, since it is necessary to remove the solvent by heating in the subsequent step. Further, if the concentration is too high, the viscosity tends to be high, and the uniform mixing property of the lithium-containing composite oxide with the composition (1) will be decreased. Accordingly, the concentration of the water soluble compound (1) contained in the composition (1) is preferably from 0.5 to 30 mass %, particularly preferably from 2 to 20 mass % as calculated as the metal element (m).
- the concentration of the water soluble compound (2) contained in the composition (2) is also preferably higher, since it is necessary to remove the solvent by heating in the subsequent step. Further, in the same manner as the composition (1), if the concentration is too high, the viscosity tends to be high, and the uniform mixing property of the lithium-containing composite oxide with the composition (2) will be decreased. Accordingly, the concentration of the water soluble compound (2) contained in the composition (2) is preferably from 0.5 to 30 mass %, particularly preferably from 2 to 20 mass % as calculated as the anion N.
- the total amount A (ml/100 g) of the composition (1) and the composition (2) to be contacted per 100 g of the lithium-containing composite oxide is within a range of 0.1 ⁇ A/B ⁇ 5 to the oil absorption B (ml/100 g) of the lithium-containing composite oxide.
- the oil absorption B is obtained in accordance with the method as disclosed in JIS-K-5101-13-1:2004.
- the ratio (A/B) is within a range of the formula ⁇ 0.1 ⁇ A/B ⁇ 5 ⁇ , the after-mentioned covering layer (I) can uniformly be formed, filtration will be unnecessary, and further, the solvent to be evaporated at the time of heating is small, thus improving productivity.
- the ratio (A/B) is within a range of the formula ⁇ 0.1 ⁇ A/B ⁇ 0.7 ⁇ , whereby the lithium-containing composite oxide will not be agglomerated at the time of spray coating, and stirring will easily be conducted.
- the above ratio (A/B) is at least 0.7, it is preferred to contact the composition (1) and the composition (2) with the lithium-containing composite oxide with drying so as to prevent the lithium-containing composite oxide from being agglomerated.
- Spray coating and drying may be carried out alternately, or spray coating may be carried out with heating for dying simultaneously.
- the drying temperature is preferably from 40 to 200° C., more preferably from 60 to 150° C.
- the lithium-containing composite oxide is agglomerated, it is preferably pulverized.
- the discharge amount of the composition (1) and the composition (2) in the spray coating method is preferably from 0.005 to 0.1 g/min per 1 g of the lithium-containing composite oxide.
- the ratio of ⁇ the amount of the composition (1)/the amount of the composition (2) ⁇ is preferably within a range of from 0.1 to 10, particularly preferably within a range of from 0.25 to 4, whereby the mixing property of the composition (1) and the composition (2) with the lithium-containing composite oxide will be good.
- the composition (1) or the composition (2) is contacted with the lithium-containing composite oxide by adding the composition (1) or the composition (2) to the lithium-containing composite oxide with stirring and mixing them.
- a stirring apparatus a stirring machine with low shearing force such as a drum mixer or solid air may be employed.
- the lithium-containing composite oxide is contacted with the composition (1) and the composition (2), and they are heated. By heating, the desired cathode active material is obtained and in addition, volatile impurities such as water and organic components can be removed. It is preferred to contact the composition (1) and the composition (2) with the lithium-containing composite oxide, and to dry and heat them while the entire amount of the composition (1) and the composition (2) are supported, without filtration and the like.
- Heating is preferably carried out in an oxygen-containing atmosphere.
- the heating temperature is preferably from 250 to 700° C., more preferably from 350 to 600° C.
- the heating temperature is at least 250° C.
- the after-mentioned covering layer (I) containing the metal element (m) and the anion N is likely to be formed. Further, volatile impurities such as remaining water tend to be small, whereby a decrease in the cycle characteristics can be suppressed.
- the heating temperature is at most 700° C., it is possible to prevent a decrease of the capacity by diffusion of the metal element (m) into the inside of the cathode active material of the present invention.
- the heating temperature is preferably from 250 to 550° C., more preferably from 350 to 500° C.
- the heating temperature is at most 550° C., the after-mentioned covering layer (I) will hardly be crystallized.
- the heating time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 18 hours, particularly preferably from 1 to 12 hours.
- the heating time is within the above range, it is possible to efficiently cover the surface of the lithium-containing composite oxide with the after-mentioned covering layer (I).
- the pressure at the time of heating is not particularly limited, preferably normal pressure or elevated pressure, particularly preferably normal pressure.
- the cathode active material produced by the production process of the present invention is particles (II) having a covering layer (I) containing the metal element (m) and the anion N formed on the surface of the lithium-containing composite oxide containing Li element and a transition metal element.
- the covering layer (I) is formed by the composition (1) and the composition (2) used in the above production process. That is, the covering layer (I) contains the anion N having the metal element (m) and the element (n).
- the covering layer (I) preferably comprises a hardly soluble salt having the cation M having the metal element (m) and the anion N bonded by ionic bond.
- hardly soluble means a solubility (the mass [g] of a solute dissolved in 100 g of a saturated solution) in distilled water at 25° C. of from 0 to 2.
- solubility is from 0 to 2
- the salt is highly stable and hardly adsorbs moisture, whereby impurities such as moisture will not remain, and the cycle characteristics will improve.
- the solubility of the hardly soluble salt is more preferably from 0 to 1, whereby the above effect will be remarkable, and is particularly preferably from 0 to 0.5.
- anion N the above anion N may similarly be used, and the preferred embodiments are also the same.
- the covering layer (I) may, for example, be specifically BaSO 4 , CaSO 4 , PbSO 4 , SrSO 4 , AlPO 4 , LaPO 4 , Ce 3 (PO 4 ) 4 , Mg 3 (PO 4 ) 2 , Li 3 (PO 4 ) 2 , Ba 3 (PO 4 ) 2 , Zr 3 (PO 4 ) 4 , Nb 3 (PO 4 ) 5 , Ca 3 (PO 4 ) 2 , Ba 3 (PO 4 ) 2 , CePO 4 , BiPO 4 , LaF 3 , AlF 3 , LiF, SrF 2 , BaF 2 , CeF 3 , InF 3 , MgF 2 , MgF 2 , CaF 2 , ZrF 4 , NbF 3 or NbF 5 , but is not particularly limited.
- the covering layer (I) contains an oxide
- preferred is Al 2 O 3 , ZrO 2 , Nb 2 O 3 or Nb 2 O 5
- preferred is Al(OH) 3 , Zr(OH) 4 , Nb(OH) 3 or Nb(OH) 5
- particularly preferred is Al(OH) 3 .
- covering layer (I) one or more types of the above compounds may be employed.
- the covering layer (I) may contain a lithium salt formed by reaction of lithium ion contained in the lithium-containing composite oxide and the anion N.
- the lithium salt may, for example, be LiF, Li 3 PO 4 or Li 2 SO 4 .
- the cathode active material obtained by the production process of the present invention it is considered that by the covering layer (I), contact of the lithium-containing composite oxide with the electrolytic solution can be reduced, and accordingly the elution of the transition metal element such as Mn from the lithium-containing composite oxide surface to the electrolytic solution is suppressed, and the cycle characteristics will be improved. Further, it is possible to prevent a decomposed product of the electrolytic solution from being attached to the surface of the lithium-containing composite oxide, whereby the rate characteristics are considered to be improved.
- the covering layer (I) may be crystalline or may be amorphous, and is preferably amorphous.
- amorphous means that no peak attributable to the covering layer (I) is observed in X-ray diffraction measurement (hereinafter sometimes referred to as XRD). The reason is not clearly understood, but is considered as follows.
- the covering layer (I) is likely to be eluted to the electrolytic solution and functions as a sacrificial layer, whereby elution of the transition metal element such as Mn on the surface of the lithium-containing composite oxide to the electrolytic solution can be suppressed, and the cycle characteristics will be improved.
- the average particle size of the covering layer (I) is preferably from 0.1 to 100 nm, more preferably from 0.1 to 50 nm, particularly preferably from 0.1 to 30 nm.
- the shape and the average particle size of the covering layer (I) can be evaluated by an electron microscope such as a SEM (scanning electron microscope) or a TEM (transmission electron microscope).
- the average particle size is represented by an average of particle sizes of particles covering the surface of the lithium-containing composite oxide.
- the particles (II) in the present invention are particles having the surface of the lithium-containing composite oxide covered with the covering layer (I).
- “covered” means a state where the covering layer (I) is chemically adsorbed or physically adsorbed to a part of or the entire surface of the lithium-containing composite oxide.
- the shape of the particles (II) may be the form of particles, a film, fibers, agglomerates or the like.
- the average particle size of the particles (II) is preferably from 3 to 30 ⁇ m, more preferably from 4 to 25 ⁇ m, particularly preferably from 5 to 20 ⁇ m.
- the particles (II) at least part of the surface of the lithium-containing composite oxide is covered with the covering layer (I).
- the particles (II) are preferably particles having a part of or the entire surface of the particles (II) covered with an amorphous layer of the covering layer (I).
- the surface of the lithium-containing composite oxide being covered with the covering layer (I) can be evaluated, for example, by cutting a particle (II), then polishing the cross-section, followed by elemental mapping by X-ray microanalyzer analysis (EPMA).
- EPMA X-ray microanalyzer analysis
- the amount (molar ratio) of the metal element (m) in the covering layer (I) is preferably from 0.001 to 0.05, more preferably from 0.003 to 0.04, particularly preferably from 0.005 to 0.03 to the transition metal element in the lithium-containing composite oxide.
- a cathode active material having a large discharge capacity and excellent rate characteristics and cycle characteristics will be obtained.
- the amount (molar ratio) of the anion N in the covering layer (I) is preferably from 0.001 to 0.05, more preferably from 0.003 to 0.04, particularly preferably from 0.005 to 0.03 to the transition metal element in the lithium-containing composite oxide.
- the amount (mol) of the metal element (m) in the covering layer (I) ⁇ the average valence of the metal element (m))/(the amount (mol) of the anion N in the covering layer (I) ⁇ the average valence of the anion N) is preferably from 0.1 to 10, more preferably from 0.2 to 4, particularly preferably from 0.3 to 2. Within such a range, excellent cycle characteristics and rate characteristics will be obtained.
- the charge and discharge efficiency will improve, and accordingly it is preferably from 0.1 to 0.99, more preferably from 0.2 to 0.9, particularly preferably from 0.3 to 0.8. It is considered that since the negative charge by the anion N is more significant than the positive charge by the metal element (m), the excess lithium ions contained in the lithium-containing composite oxide are bonded to the anion N, whereby the charge and discharge efficiency will improve.
- the amount (mol) of the metal element (m) present in the covering layer (I) in the particles (II) can be measured by ICP (inductively coupled plasma) measurement of the cathode active material dissolved in an acid. In a case where the amount (mol) of the metal element (m) present in the covering layer (I) cannot be obtained by the ICP measurement, it may be calculated based on the amount of the metal element (m) in the lithium-containing composite oxide and the composition (1).
- the amount (mol) of the anion N present in the covering layer (I) in the particles (II) can be measured by ion chromatography measurement of the cathode active material dissolved in an acid. In a case where the amount (mol) of the anion N present in the covering layer (I) cannot be obtained by the ion chromatography measurement, it may be calculated based on the amount of the element (n) in the lithium-containing composite oxide and the composition (2).
- the cathode active material of the present invention which has the covering layer (I) on at least part of the surface of the lithium-containing composite oxide, has a high discharge capacity and excellent rate characteristics and cycle characteristics.
- the cathode for a lithium ion secondary battery of the present invention comprises a cathode active material layer containing the above cathode active material of the present invention, an electrically conductive material and a binder formed on a cathode current collector (cathode surface).
- a method for producing the cathode for a lithium ion secondary battery for example, a method of supporting the cathode active material of the present invention, an electrically conductive material and a binder on a cathode current collector may be mentioned.
- the electrically conductive material and the binder can be supported on a cathode current collector by dispersing them in a solvent and/or a dispersion medium to prepare a slurry, or kneading them with a solvent and/or a dispersion medium to prepare a kneaded product, and applying the prepared slurry or kneaded product to the cathode current collector e.g. by coating.
- the electrically conductive material may, for example, be carbon black such as acetylene black, graphite or ketjen black.
- the binder may, for example, be a fluorinated resin such as polyvinylidene fluoride or polytetrafluoroethylene, a polyolefin such as polyethylene or polypropylene, a polymer or copolymer containing unsaturated bonds such as styrene/butadiene rubber, isoprene rubber or butadiene rubber, or an acrylic acid type polymer or copolymer such as an acrylic acid copolymer or a methacrylic acid copolymer.
- a fluorinated resin such as polyvinylidene fluoride or polytetrafluoroethylene
- a polyolefin such as polyethylene or polypropylene
- a polymer or copolymer containing unsaturated bonds such as styrene/butadiene rubber, isoprene rubber or butadiene rubber
- an acrylic acid type polymer or copolymer such as an acrylic acid copolymer or a methacrylic acid copo
- the cathode current collector may be aluminum or an aluminum alloy.
- the lithium ion secondary battery of the present invention comprises the cathode for a lithium ion secondary battery of the present invention, an anode and a non-aqueous electrolyte.
- the anode comprises an anode current collector and an anode active material layer containing an anode active material formed on the anode current collector. It can be produced, for example, by kneading an anode active material with an organic solvent to prepare a slurry, and applying the prepared slurry on the anode current collector, followed by drying and pressing.
- the anode current collector may, for example, be a metal foil such as a nickel foil or a copper foil.
- the anode active material is a material capable of adsorbing and desorbing lithium ions at a relatively low potential and may, for example, be lithium metal, a lithium alloy, a carbon material, an oxide consisting mainly of a metal in Group 14 or 15 of the periodic table, a carbon compound, a silicon carbide compound, a silicon oxide compound, titanium sulfide or a boron carbide compound.
- the carbon material for the anode active material may, for example, be non-graphitizable carbon, artificial carbon, natural graphite, thermally decomposed carbon, cokes such as pitch coke, needle coke or petroleum coke, graphites, glassy carbons, an organic polymer compound fired product obtained by firing and carbonizing a phenol resin, furan resin, etc. at a suitable temperature, carbon fibers, activated carbon or carbon blacks.
- the metal in Group 14 of the periodic table may, for example, be silicon or tin, and is most preferably silicon.
- a material which may be used as the anode active material may, for example, be an oxide such as iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide or tin oxide, or a nitride such as Li 2.6 Co 0.4 N.
- non-aqueous electrolytic solution it is possible to use one prepared by suitably combining an organic solvent and an electrolyte.
- organic solvent any solvent known as an organic solvent for an electrolytic solution may be used, and for example, it is possible to use propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme, triglyme, ⁇ -butyrolacton diethyl ether, sulfolan, methyl sulfolan, acetonitrile, an acetic acid ester, a butylic acid ester, a propionic acid ester, etc.
- a cyclic carbonate such as propylene carbonate, or a chain-structured carbonate such as dimethyl carbonate or diethyl carbonate.
- organic solvents may be used alone, or two or more of them may be used as mixed.
- non-aqueous electrolyte it is possible to use a solid electrolyte containing an electrolyte salt, a polymer electrolyte, a solid or gelled electrolyte having an electrolyte mixed or dissolved in e.g. a polymer compound, etc.
- the solid electrolyte may be any material so long as it has lithium ion conductivity, and for example, either an inorganic solid electrolyte or a polymer electrolyte may be used.
- the inorganic solid electrolyte it is possible to use lithium nitride, lithium iodide, etc.
- polymer electrolyte it is possible to use e.g. an electrolyte salt and a polymer compound which dissolves the electrolyte salt.
- polymer compound which dissolves the electrolyte salt it is possible to use polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, or a derivative, mixture or composite thereof.
- any polymer material which is gelled upon absorption of the above non-aqueous electrolytic solution may be employed.
- the polymer material may, for example, be a fluorinated polymer material such as poly(vinylidene fluoride) or poly(vinylidene fluoride-co-hexafluoropropylene), polyacrylonitrile, a copolymer of polyacrylonitrile, or an ether type polymer material such as polyethylene oxide or a copolymer or cross-linked product of polyethylene oxide.
- the monomer to be copolymerized may, for example, be polypropylene oxide, methyl methacrylate, butyl methacrylate, methyl acrylate or butyl acrylate.
- the gelled electrolyte particularly preferred is a fluorinated polymer material from the viewpoint of the stability against the redox reaction.
- any electrolyte salt to be used for this type of battery may be used, and for example, LiClO 4 , LiPF 6 , LiBF 4 or CF 3 SO 3 Li may be used.
- the shape of the lithium ion secondary battery of the present invention may be suitably selected depending on the intended use from e.g. a coin-shape, a sheet-form (film-form), a folded shape, a wound cylinder with bottom, a button shape, etc.
- the process for producing a cathode active material for a lithium ion secondary battery of the present invention it is possible to produce a cathode active material for a lithium ion secondary battery having excellent cycle characteristics and rate characteristics even when discharging is carried out at a high voltage, with good productivity. Further, according to the production process of the present invention, filtration and washing are unnecessary, the lithium-containing composite oxide will not be agglomerated and handling such as stirring is easy, and further, agglomeration is less likely to occur at the time of drying, whereby the productivity will remarkably improve.
- the cathode active material for a lithium ion secondary battery obtained by the production process of the present invention has excellent cycle characteristics and rate characteristics even when discharging is carried out at a high voltage. Further, a cathode for a lithium ion secondary battery using the cathode active material, and a lithium ion secondary battery using the cathode, can realize excellent cycle characteristics and rate characteristics even when discharging is carried out at a high voltage.
- Distilled water (1,245.9 g) was added to nickel(II) sulfate hexahydrate (140.6 g), cobalt(II) sulfate heptahydrate (131.4 g) and manganese(II) sulfate pentahydrate (482.2 g) to obtain a raw material solution.
- Distilled water (320.8 g) was added to ammonium sulfate (79.2 g) to obtain an ammonia solution.
- Distilled water (1,920.8 g) was added to ammonium sulfate (79.2 g) to obtain a mother liquid.
- sodium hydroxide (400 g) was uniformly dissolved to obtain a pH-adjusting liquid.
- the mother liquid was put and heated to 50° C. by a mantle heater, and the pH-adjusting liquid was added to bring the pH to be 11.0.
- the raw material solution was added at a rate of 5.0 g/min, and the ammonia solution was added at a rate of 1.0 g/min, to have a composite hydroxide of nickel, cobalt and manganese precipitated.
- the pH-adjusting liquid was added to maintain the pH in the reactor to be 11.0.
- nitrogen gas was introduced into the reactor at a flow rate of 0.5 L/min. Further, the liquid was continuously withdrawn so that the liquid amount in the reactor would not exceed 2 L.
- the precursor (20 g) and lithium carbonate (12.6 g) having a lithium content of 26.9 mol/kg were mixed and fired at 900° C. for 12 hours in an oxygen-containing atmosphere to obtain a lithium-containing composite oxide in Synthesis Example.
- the composition of the obtained lithium-containing composite oxide in Synthesis Example was Li(Li 0.2 Ni 0.137 Co 0.125 Mn 0.538 )O 2 .
- the lithium-containing composite oxide in Synthesis Example had an average particle size D50 of 5.9 ⁇ m, and a specific surface area of 2.6 m 2 /g as measured by means of BET (Brunauer, Emmett, Teller) method.
- the oil absorption was measured using purified linseed oil in accordance with JIS-K-5101-13-1:2004, whereupon it was 44 (g/100 g).
- composition (1) 3.0 g of distilled water was added to 7.0 g of an aluminum lactate aqueous solution (Al content: 4.5 mass %, pH: 4.6) to prepare an aqueous aluminum solution (composition (1)). Further, 7.7 g of distilled water was added to 2.3 g of (NH 4 ) 2 HPO 4 to prepare a phosphate aqueous solution (composition (2)).
- Example 1 a cathode active material in Example 1 comprising particles (II) having a covering layer (I) containing the metal element Al and the anion PO 4 3 ⁇ formed on the surface of the lithium-containing composite oxide.
- XRD measurement using CuK ⁇ rays as an X-ray source was carried out.
- RINT-TTR-III tradename, manufactured by Rigaku Corporation was used.
- the covering layer (I) is amorphous.
- Example 2 As the composition (2), 9.57 g of distilled water was added to 0.43 g of NH 4 F to prepare an ammonium fluoride aqueous solution. In the same manner as in Example 1 except that the ammonium fluoride aqueous solution was used instead of the phosphate aqueous solution, a cathode active material in Example 2 comprising particles (II) having a covering layer (I) containing the metal element Al and the anion F ⁇ formed on the surface of the lithium-containing composite oxide was obtained.
- the covering layer (I) is considered to be a gradient film comprising Al 2 O 3 in the inside, AlF 3 on the outside and AlOF in the middle.
- Example 3 As the composition (2), 8.70 g of distilled water was added to 1.30 g of NH 4 F to prepare an ammonium fluoride aqueous solution.
- a cathode active material in Example 3 comprising particles (II) having a covering layer (I) containing the metal element Al and the anion F ⁇ formed on the surface of the lithium-containing composite oxide was obtained.
- Example 4 As the composition (2), 7.40 g of distilled water was added to 2.60 g of NH 4 F to prepare an ammonium fluoride aqueous solution.
- a cathode active material in Example 4 comprising particles (II) having a covering layer (I) containing the metal element Al and the anion F ⁇ formed on the surface of the lithium-containing composite oxide was obtained.
- the lithium-containing composite oxide in Synthesis Example was used as the cathode active material in Comparative Example 2 as it was without covering treatment.
- Example 1 The procedure in Example 1 was changed, and the aluminum aqueous solution and the phosphate aqueous solution were mixed, whereupon a gel was precipitated, whereby the mixture could not be sprayed to the lithium-containing composite oxide.
- each of the cathode active materials in Examples 1 to 4 and Comparative Examples 1 and 2 as the cathode active material, acetylene black (electrically conductive material) and a polyvinylidene fluoride solution (solvent: N-methylpyrrolidone) containing 12.1 mass % of polyvinylidene fluoride (binder) were mixed, and N-methylpyrrolidone was further added to prepare a slurry.
- the mass ratio of the cathode active material, acetylene black and polyvinylidene fluoride was 82/10/8.
- cathode current collector aluminum foil having a thickness of 20 ⁇ m by means of a doctor blade, followed by drying at 120° C. and roll pressing twice to prepare a cathode sheet.
- Cathode sheets obtained from the cathode active materials in Examples 1 to 4 are regarded as cathode sheets 1 to 4, respectively, and cathode sheets obtained from the cathode active materials in Comparative Examples 1 and 2 are regarded as cathode sheets 5 and 6.
- a stainless steel simple sealed cell type lithium ion secondary battery was assembled in an argon globe box.
- a metal lithium foil having a thickness of 500 ⁇ m was used as an anode
- a stainless steel plate having a thickness of 1 mm was used as an anode current collector
- a porous propylene having a thickness of 25 ⁇ m was used as a separator
- Lithium ion secondary batteries obtained by using the cathode sheets 1 to 6 are regarded as lithium batteries 1 to 6, respectively.
- the battery was charged to 4.6 V with a load current of 200 mA per 1 g of the cathode active material, and then discharged to 2.5 V with a load current of 100 mA per 1 g of the cathode active material.
- the discharge capacity of the cathode active material at from 4.6 to 2.5 V was taken as the 4.6 V initial capacity. Further, a value obtained by dividing the discharge capacity by the charge capacity was taken as the initial charge and discharge efficiency.
- the battery was charged to 4.6 V with a load current of 200 mA per 1 g of the charged and discharged cathode active material, and then discharged to 2.5 V at high rate with a load current of 400 mA per 1 g of the cathode active material.
- a value obtained by dividing the discharge capacity of the cathode active material at from 4.6 to 2.5 V at high rate discharging by the 4.6 V initial capacity was taken as the rate retention rate.
- the metal salt/anion ratio is (the total amount of the cation M contained in the composition (1) ⁇ the average valence of the cation M)/(the total amount of the anion N contained in the composition (2) ⁇ the average valence of the anion N).
- each of the lithium batteries 1 to 4 using the cathode active material comprising particles (II) covered with the covering layer (I) has a high initial capacity and a high initial charge and discharge efficiency and has an excellent cycle retention rate as compared with the lithium battery 6 using the cathode active material in Comparative Example 2 not covered.
- each of the lithium batteries 1 to 4 using the cathode active material comprising particles (II) covered with the covering layer (I) has a high initial capacity and a high initial charge and discharge efficiency and has an excellent rate retention rate as compared with the lithium battery 5 using the cathode active material in Comparative Example 1 covered only with Al.
- each lithium-containing composite oxide the aluminum aqueous solution and the phosphate aqueous solution (composition (2)) were sprayed in the same manner as in Example 1.
- Cathode active materials comprising particles (II) covered with the covering layer (I) were obtained under conditions where the lithium-containing composite oxide would not be agglomerated and handling such as stirring would be easy, or under conditions where the lithium-containing composite oxide would be agglomerated and handling such as stirring would be difficult, by changing ⁇ (the total amount A of the composition (1) and the composition (2) contacted per 100 g of the lithium-containing composite oxide)/(the oil absorption B of the lithium-containing composite oxide) ⁇ .
- Example 5 The evaluation results in Example 5 are shown in the graph in FIG. 1 and the following Table 2.
- cathode active material for a lithium ion secondary battery having a high discharge capacity per unit mass and having excellent cycle characteristics and rate characteristic.
- the cathode active material is useful for lithium ion secondary batteries for electronic instruments such as mobile phones, and for vehicles, which are small in size and light in weight.
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Abstract
Description
- Patent Document 1: JP-A-2008-536285
- Patent Document 2: Japanese Patent No. 4582990
- Patent Document 3: WO2007/102407
[6] The process for producing a cathode active material for a lithium ion secondary battery according to any one of [1] to [4], wherein the amount (molar ratio) of the anion N contained in the composition (2) is within a range of from 0.001 to 0.05 based on the total amount of the transition metal element contained in the lithium-containing composite oxide.
[7] The process for producing a cathode active material for a lithium ion secondary battery according to any one of [1] to [6], wherein contact of the lithium-containing composite oxide with the composition (1) or the composition (2) is carried out by adding the composition (1) or the composition (2) to the lithium-containing composite oxide with stirring and mixing the lithium-containing composite oxide and the composition (1) or the composition (2).
[8] The process for producing a cathode active material for a lithium ion secondary battery according to any one of [1] to [7], wherein contact of the lithium-containing composite oxide with the composition (1) or the composition (2) is carried out by spraying the composition (1) or the composition (2) to the lithium-containing composite oxide by a spray coating method.
[9] A cathode for a lithium ion secondary battery, which comprises a cathode active material for a lithium ion secondary battery produced by the production process as defined in any one of [1] to [8], and a binder.
[10] A lithium ion secondary battery comprising the cathode as defined in [9], an anode and a non-aqueous electrolyte.
(Compound (i))
Lia(NixMnyCoz)MebO2 (1)
(Compound (ii))
LiLXx.Yy.Oz.Fg (2)
Li(LixMnyMe′z)OpFq (3-1)
Li(LixMnyNivCow)Op (3-2)
Li(Mn2-xMe″x)O4 (4)
TABLE 1 | ||||||||
Initial | ||||||||
Metal | charge | Rate | Cycle | |||||
salt/ | 4.6 V | and | reten- | reten- | ||||
Metal | Anion | anion | initial | discharge | tion | tion | ||
salt M | N | ratio | capacity | efficiency | rate | rate | ||
Lithium | Al3+ | PO4 3− | 1.0 | 220 | 73% | 83% | 88 |
battery | |||||||
1 | |||||||
Lithium | Al3+ | F− | 0.33 | 215 | 68% | 82% | 89 |
battery | |||||||
2 | |||||||
Lithium | Al3+ | F− | 1.0 | 216 | 70% | 83% | 87% |
battery 3 | |||||||
Lithium | Al3+ | F− | 2.0 | 221 | 75% | 83% | 86% |
battery 4 | |||||||
Lithium | Al3+ | — | — | 207 | 66% | 81% | 86% |
battery 5 | |||||||
Lithium | — | — | — | 210 | 67% | 82% | 70% |
battery 6 | |||||||
TABLE 2 | ||||
A with | A with | |||
which lithium- | which lithium- | |||
containing | containing | |||
Oil | composite oxide | composite oxide | ||
absorp- | would not be | would be | ||
tion B | agglomerated | agglomerated | ||
[g/100 g] | [g/100 g] | [g/100 g] | ||
Lithium-containing | 52 | 30 | 40 |
composite oxide | |||
(fired at 800° C.) | |||
Lithium-containing | 44 | 20 | 36 |
composite oxide | |||
(fired at 900° C.) | |||
Lithium-containing | 41 | 20 | 32 |
composite oxide | |||
(fired at 1,000° C.) | |||
Commercially | 19 | 8 | 20 |
available ternary | |||
lithium-containing | |||
composite oxide | |||
Commercially | 12 | 4 | 16 |
available lithium | |||
cobaltate | |||
Claims (12)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011140493 | 2011-06-24 | ||
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